TW201705267A - Plasma etching method, pattern forming method, and cleaning method - Google Patents

Plasma etching method, pattern forming method, and cleaning method Download PDF

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TW201705267A
TW201705267A TW105109936A TW105109936A TW201705267A TW 201705267 A TW201705267 A TW 201705267A TW 105109936 A TW105109936 A TW 105109936A TW 105109936 A TW105109936 A TW 105109936A TW 201705267 A TW201705267 A TW 201705267A
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film
zirconia
plasma
gas
etching
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TW105109936A
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TWI715563B (en
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味上俊一
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東京威力科創股份有限公司
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
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    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
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    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
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    • H01L21/32137—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas of silicon-containing layers

Abstract

An object of the invention is to provide a method of forming a pattern on a film with a favorable selectivity relative to a specific etching target film. The invention provides a plasma etching method that includes a step of etching a film comprising zirconium oxide in a desired pattern formed in a first mask using a plasma generated from a gas composed of hydrogen bromide (HBr) and one or other of boron trichloride (BCl3) and silicon tetrachloride (SiCl4), wherein the base film of the zirconium oxide film is a silicon oxide film or amorphous carbon, and the etching selectivity of the zirconium oxide film with respect to the base film is at least one.

Description

電漿蝕刻方法、圖案形成方法及清洗方法Plasma etching method, pattern forming method and cleaning method

本發明係有關於電漿蝕刻方法、圖案形成方法及清洗方法。The present invention relates to a plasma etching method, a pattern forming method, and a cleaning method.

已知一種技術，係從氣體產生電漿，而藉由電漿蝕刻以對所要蝕刻之膜進行微細加工。例如於專利文獻1揭露有一種技術，係藉由熱氧化處理而在基板上形成矽氧化膜後，藉由CVD（Chemical Vapor Deposition；化學氣相沈積）以形成High－k膜，再使用Cl2 等氣體所產生之電漿以蝕刻High－k膜。再者，於專利文獻2揭露有一種技術，係使用BCl3 氣體所產生之電漿以蝕刻High－k膜。A technique is known in which a plasma is generated from a gas and plasma etching is performed to finely process the film to be etched. For example, Patent Document 1 discloses a technique in which a tantalum oxide film is formed on a substrate by thermal oxidation treatment, followed by CVD (Chemical Vapor Deposition) to form a High-k film, and then Cl 2 is used. The plasma generated by the gas is etched to etch the High-k film. Further, Patent Document 2 discloses a technique of etching a High-k film by using a plasma generated by BCl 3 gas.

此外，近年來需求一種蝕刻技術，要藉由電漿蝕刻而在矽氧化膜或非晶質碳膜般特定之所要蝕刻之膜，形成很深的深孔或凹溝。 ［習知技術文獻］ ［專利文獻］Further, in recent years, an etching technique has been demanded to form a deep deep hole or a groove by plasma etching in a film which is specifically etched like a tantalum oxide film or an amorphous carbon film. [Practical Technical Literature] [Patent Literature]

［專利文獻1］日本特開2005－252186號公報 ［專利文獻2］日本特開2004－146787號公報[Patent Document 1] JP-A-2005-252186 (Patent Document 2) JP-A-2004-146787

［發明所欲解決的問題］ 然而，若所要蝕刻之膜相對於High－k膜等所要蝕刻之膜之基底膜，難以獲得充分的蝕刻選擇比，則難以在High－k膜等所要蝕刻之膜上形成深且垂直之深孔或凹溝，蝕刻特性不佳。[Problems to be Solved by the Invention] However, if the film to be etched is difficult to obtain a sufficient etching selectivity ratio with respect to the base film of the film to be etched such as a High-k film or the like, it is difficult to form a film to be etched in a High-k film or the like. Deep and vertical deep holes or grooves are formed on the upper surface, and the etching characteristics are not good.

有鑑於上述課題，本發明之一個層面，係以提供一種對膜層進行電漿蝕刻的方法為目的，該膜層包含一膜層，其相對於特定之所要蝕刻之膜具有良好的選擇比。 ［解決問題之技術手段］In view of the above problems, one aspect of the present invention is directed to providing a method of plasma etching a film layer comprising a film layer having a good selectivity with respect to a particular film to be etched. [Technical means to solve the problem]

為解決上述課題，根據本發明一態樣，提供一種電漿蝕刻方法，包括一步驟，其藉由三氯化硼BCl3 或四氯化矽SiCl4 中之任一、以及溴化氫HBr構成之氣體所產生之電漿，而對包含氧化鋯膜之膜層進行蝕刻，以蝕刻成在第1遮罩上所形成之所要的圖案；在該電漿蝕刻方法，該氧化鋯膜之基底膜係矽氧化膜或非晶質碳，而氧化鋯膜相對於該基底膜的蝕刻選擇比係1以上。 ［發明之效果］In order to solve the above problems, according to an aspect of the present invention, a plasma etching method comprising a step of forming any one of boron trichloride BCl 3 or hafnium tetrachloride SiCl 4 and hydrogen bromide HBr is provided. a plasma generated by the gas, and etching a film layer containing the zirconia film to be etched into a desired pattern formed on the first mask; in the plasma etching method, the base film of the zirconia film The tantalum oxide film or amorphous carbon is used, and the etching selectivity of the zirconia film with respect to the base film is 1 or more. [Effects of the Invention]

根據本發明一態樣，可以進行膜層之電漿蝕刻，該膜層包含一膜層，其相對於特定之所要蝕刻之膜具有良好的選擇比。According to one aspect of the invention, plasma etching of the film layer can be performed, the film layer comprising a film layer having a good selectivity to the particular film to be etched.

以下，針對用以實施本發明之形態，參照圖式進行說明。又，於本明細書及圖式中，對於實質相同之結構，會標註相同符號，而省略重複說明。又，針對壓力値，可將1Torr換算為133.322Pa。Hereinafter, the form for carrying out the invention will be described with reference to the drawings. In the present invention, the same reference numerals will be given to the same structures, and the repeated description will be omitted. Further, for the pressure enthalpy, 1 Torr can be converted into 133.322 Pa.

［電漿蝕刻裝置之概略結構］ 首先，針對本發明一實施形態之電漿蝕刻裝置的結構，參照圖1以進行說明。圖1係繪示一實施形態之電漿蝕刻裝置之概略結構的縱剖面圖。[Schematic Structure of Plasma Etching Apparatus] First, the structure of a plasma etching apparatus according to an embodiment of the present invention will be described with reference to Fig. 1 . Fig. 1 is a longitudinal cross-sectional view showing a schematic configuration of a plasma etching apparatus according to an embodiment.

於圖1所示之電漿蝕刻裝置1，具有例如鋁或不鏽鋼等金屬製之圓筒型處理室（以下，僅稱為處理室C。）。處理室C有施行接地。於處理室C內，對半導體晶圓（以下稱為晶圓W。）實施電漿蝕刻處理。The plasma etching apparatus 1 shown in Fig. 1 has a cylindrical processing chamber made of a metal such as aluminum or stainless steel (hereinafter, simply referred to as a processing chamber C). The processing chamber C is grounded. A plasma etching process is performed on the semiconductor wafer (hereinafter referred to as wafer W) in the processing chamber C.

處理室C（處理室）內設有載置晶圓W的載置台2。載置台2亦發揮下部電極之功能。於處理室C之天花板處，配置著與載置台2相向的上部電極3。上部電極3連接著氣體供給源4。於上部電極3的內部，形成擴散室3a，使來自氣體供給源4的氣體擴散。擴散室3a內的氣體，通過設於上部電極3底部的許多氣體孔3b，而導入至處理室C內。上部電極3亦發揮用以供給氣體之簇射頭的功能。A mounting table 2 on which the wafer W is placed is provided in the processing chamber C (processing chamber). The mounting table 2 also functions as a lower electrode. The upper electrode 3 facing the mounting table 2 is disposed on the ceiling of the processing chamber C. The upper electrode 3 is connected to the gas supply source 4. Inside the upper electrode 3, a diffusion chamber 3a is formed to diffuse gas from the gas supply source 4. The gas in the diffusion chamber 3a is introduced into the processing chamber C through a plurality of gas holes 3b provided at the bottom of the upper electrode 3. The upper electrode 3 also functions as a shower head for supplying gas.

於電漿蝕刻裝置1，設有第1高頻電源5及第2高頻電源6。從第1高頻電源5輸出之產生電漿用的高頻電力，係施加至載置台2（下部電極）。又，來自第1高頻電源5的高頻電力，可以係施加至下部電極，亦可以係施加至上部電極。從第2高頻電源6輸出之偏壓用的高頻電力，係施加至載置台2。The plasma etching apparatus 1 is provided with a first high frequency power source 5 and a second high frequency power source 6. The high-frequency power for generating plasma generated from the first high-frequency power source 5 is applied to the mounting table 2 (lower electrode). Further, the high-frequency power from the first high-frequency power source 5 may be applied to the lower electrode or may be applied to the upper electrode. The high frequency power for bias voltage output from the second high frequency power source 6 is applied to the mounting table 2.

導入至處理室C內的氣體，會由於所施加之高頻電力而電漿化。藉此而在處理室C內，施行對晶圓W所進行之電漿蝕刻、或清洗等的電漿處理。本實施形態之電漿蝕刻方法、圖案形成方法及清洗方法，可以使用此結構之電漿蝕刻裝置1來執行。The gas introduced into the processing chamber C is plasmad due to the applied high frequency power. Thereby, plasma processing such as plasma etching or cleaning of the wafer W is performed in the processing chamber C. The plasma etching method, pattern forming method, and cleaning method of the present embodiment can be performed using the plasma etching apparatus 1 of this configuration.

於電漿蝕刻裝置1，係遵照控制部7之控制以執行電漿處理。控制部7具有：CPU（Central Processing Unit；中央處理器）7a、ROM（Read Only Memory；唯讀記憶體）7b、RAM（Random Access Memory；動態隨機存取記憶體）7c等。CPU7a遵照儲存在ROM7b或RAM7c之記憶區域的各種製程配方以執行電漿處理。於製程配方記載著對應製程條件而對裝置進行之控制的資訊，如製程時間、處理室內溫度（上部電極溫度、處理室的側壁溫度、ESC溫度等）、壓力（氣體之排氣）、高頻電力及電壓、各種步驟流量、傳熱流量等。The plasma etching apparatus 1 is controlled in accordance with the control unit 7 to perform plasma processing. The control unit 7 includes a CPU (Central Processing Unit) 7a, a ROM (Read Only Memory) 7b, a RAM (Random Access Memory) 7c, and the like. The CPU 7a performs plasma processing in accordance with various process recipes stored in the memory area of the ROM 7b or the RAM 7c. The process recipe records information about the control of the device corresponding to the process conditions, such as process time, process chamber temperature (upper electrode temperature, process chamber sidewall temperature, ESC temperature, etc.), pressure (gas exhaust), high frequency Power and voltage, flow in various steps, heat transfer flow, etc.

以上針對本實施形態之電漿蝕刻裝置1的結構，進行了說明。接著將針對在電漿蝕刻裝置1對晶圓W實施電漿蝕刻之際所使用之遮罩材料，進行說明。The configuration of the plasma etching apparatus 1 of the present embodiment has been described above. Next, the mask material used when the plasma etching apparatus 1 performs plasma etching on the wafer W will be described.

［氧化鋯膜］ 於蝕刻矽氧化膜或非晶質碳膜之際，就遮罩材料而言，一般使用聚矽膜（Poly－Si）。然而，若使用聚矽膜以作為遮罩材料，會產生於蝕刻之際，相對於矽氧化膜等，無法獲得充分之聚矽膜的選擇比的課題。若無法獲得充分的選擇比，則難以在矽氧化膜等形成深且垂直的深孔。[Zirconium Oxide Film] When etching a tantalum oxide film or an amorphous carbon film, a polyimide film (Poly-Si) is generally used as the mask material. However, when a polyimide film is used as a mask material, there is a problem that a sufficient selectivity ratio of the polyimide film cannot be obtained with respect to the tantalum oxide film or the like during etching. If a sufficient selection ratio cannot be obtained, it is difficult to form deep and vertical deep holes in the tantalum oxide film or the like.

有鑑於此，於本實施形態之電漿蝕刻方法，對於矽氧化膜或非晶質碳膜這等所要蝕刻之膜的遮罩材料，係採用氧化鋯膜（ZrO）。In view of this, in the plasma etching method of the present embodiment, a zirconia film (ZrO) is used as a mask material for a film to be etched such as a tantalum oxide film or an amorphous carbon film.

於本實施形態之電漿蝕刻方法，係對晶圓W進行電漿蝕刻，該晶圓W係在矽氧化膜或非晶質碳膜上，積層有發揮遮罩之功能的氧化鋯膜。於本實施形態，提議一種電漿蝕刻方法，舉氧化鋯膜（ZrO）之基底膜係矽氧化膜或非晶質碳膜為例，而使氧化鋯膜相對於基底膜之蝕刻選擇比為1以上。In the plasma etching method of the present embodiment, the wafer W is plasma-etched, and the wafer W is formed on a tantalum oxide film or an amorphous carbon film, and a zirconia film which functions as a mask is laminated. In the present embodiment, a plasma etching method is proposed, in which a base film of a zirconium oxide film (ZrO) is an oxide film or an amorphous carbon film, and an etching selectivity ratio of the zirconium oxide film to the base film is set to 1. the above.

於下文中，將針對透過電漿蝕刻而在該結構之晶圓W上的氧化鋯膜形成所要的圖案之際之氣體的最佳化，進行說明。Hereinafter, the optimization of the gas at the time of forming a desired pattern of the zirconia film on the wafer W of the structure by plasma etching will be described.

［相對於氧化鋯膜之氣體種類］ 於本實施形態之圖案形成方法（本實施形態之電漿蝕刻方法），係由氣體產生電漿，並使用形成有所要圖案之第1遮罩（例如，光阻膜），而對含有氧化鋯膜的膜層，進行電漿蝕刻。藉此，將圖案化後之氧化鋯膜作為遮罩材料，而對矽氧化膜或非晶質碳膜進行電漿蝕刻。[Gas type with respect to zirconia film] In the pattern forming method of the present embodiment (the plasma etching method of the present embodiment), a plasma is generated from a gas, and a first mask forming a desired pattern is used (for example, The photoresist film) is subjected to plasma etching on the film layer containing the zirconia film. Thereby, the patterned zirconia film is used as a mask material, and the tantalum oxide film or the amorphous carbon film is plasma-etched.

本案發明人團隊，以本實施形態之圖案形成方法，進行了實驗，以分析出適用於在氧化鋯膜形成所要圖案之際的氣體種類。於下述實驗中，使用了圖1的電漿蝕刻裝置1。The inventor of the present invention conducted an experiment using the pattern forming method of the present embodiment to analyze the type of gas suitable for forming a desired pattern in the zirconia film. In the experiment described below, the plasma etching apparatus 1 of Fig. 1 was used.

（實驗1相對於氧化鋯膜之氣體種類：單一氣體） 於圖2繪示了以複數氣體種類而對氧化鋯膜（ZrO）、矽氧化膜（SiO2）、非晶質碳膜（α－C）進行電漿蝕刻時之蝕刻速率（Etch Rate）及選擇比（Selectivity）的實驗結果。(Experiment 1 vs. zirconia film gas type: single gas) FIG. 2 shows a zirconia film (ZrO), a tantalum oxide film (SiO2), and an amorphous carbon film (α-C) in a plurality of gas species. The experimental results of the etching rate (Etch Rate) and the selectivity (Selectivity) at the time of plasma etching.

於圖2及後述之圖3～圖7，作為所要蝕刻之膜之一例的矽氧化膜係以「Ox」代表，作為所要蝕刻之膜之另一例的非晶質碳膜係以「CUL」代表。再者，「ZrO ER」係代表氧化鋯膜的蝕刻速率，「Ox ER」係代表矽氧化膜的蝕刻速率，「CUL ER」係代表非晶質碳膜的蝕刻速率。再者，「ZrO／Ox」係代表氧化鋯膜相對於矽氧化膜的選擇比（以下稱為：選擇比「ZrO／Ox」。）。「ZrO／CUL」係代表相對於非晶質碳膜之氧化鋯膜的選擇比（以下稱為：選擇比「ZrO／CUL」。）。In Fig. 2 and Fig. 3 to Fig. 7 which will be described later, the tantalum oxide film which is an example of the film to be etched is represented by "Ox", and the amorphous carbon film which is another example of the film to be etched is represented by "CUL". . Further, "ZrO ER" represents the etching rate of the zirconia film, "Ox ER" represents the etching rate of the tantalum oxide film, and "CUL ER" represents the etching rate of the amorphous carbon film. Further, "ZrO/Ox" represents the selection ratio of the zirconia film to the tantalum oxide film (hereinafter referred to as "selection ratio "ZrO/Ox"). "ZrO/CUL" represents a selection ratio of a zirconia film to an amorphous carbon film (hereinafter referred to as "selection ratio "ZrO/CUL").

縱軸之長條圖，係氧化鋯膜相對於橫軸所示之複數氣體種類的蝕刻速率「ZrO ER」、矽氧化膜的蝕刻速率「Ox ER」、非晶質碳膜的蝕刻速率「CUL ER」。縱軸之折線圖，係相對於橫軸所示之複數氣體種類的選擇比「ZrO／Ox」、選擇比「ZrO／CUL」。The bar graph of the vertical axis is the etching rate "ZrO ER" of the zirconia film with respect to the plural gas species shown on the horizontal axis, the etching rate "Ox ER" of the tantalum oxide film, and the etching rate of the amorphous carbon film "CUL". ER". The line graph of the vertical axis is the selection ratio "ZrO/Ox" and the selection ratio "ZrO/CUL" with respect to the plural gas types shown on the horizontal axis.

本實施形態之圖案形成方法，係用於使用第1遮罩而在氧化鋯膜上形成圖案之步驟。因此，於此圖案形成步驟，較佳係不要切削到氧化鋯膜之下層膜，即矽氧化膜或非晶質碳膜。也就是說，選擇比「ZrO／Ox」、選擇比「ZrO／CUL」以高為佳。The pattern forming method of the present embodiment is a step of forming a pattern on a zirconia film by using a first mask. Therefore, in this pattern forming step, it is preferred not to cut into a film under the zirconia film, that is, a tantalum oxide film or an amorphous carbon film. In other words, the choice is better than "ZrO/Ox" and the choice is higher than "ZrO/CUL".

於圖2之實驗結果，選擇比「ZrO／Ox」及選擇比「ZrO／CUL」皆為1以上之氣體，係三氯化硼BCl3 及溴化氫HBr。尤其在以溴化氫HBr氣體所產生之電漿進行蝕刻的情況，選擇比「ZrO／CUL」為無限大。也就是說，在使用溴化氫HBr之電漿蝕刻，於蝕刻氧化鋯膜之際，完全不會切削到非晶質碳膜。As a result of the experiment in Fig. 2, a gas having a ratio of "ZrO/Ox" and a ratio of "ZrO/CUL" of 1 or more is selected, which is boron trichloride BCl 3 and hydrogen bromide HBr. In particular, in the case of etching with a plasma generated by hydrogen bromide HBr gas, the selectivity is infinitely larger than "ZrO/CUL". That is to say, in the plasma etching using hydrogen bromide HBr, the amorphous carbon film is not cut at all when the zirconia film is etched.

因此，從本實驗可知，在本實施形態之圖案形成方法中，適用於在氧化鋯膜形成所要圖案之際的氣體種類，係三氯化硼BCl3 與溴化氫HBr。Therefore, it is understood from the experiment that in the pattern forming method of the present embodiment, the type of gas applied to the desired pattern in the zirconia film is boron trichloride BCl 3 and hydrogen bromide HBr.

（實驗2相對於氧化鋯膜之氣體種類：BCl3 與HBr之比率） 其次，本案發明人團隊，變化三氯化硼BCl3 與溴化氫HBr之間的比率，而進行了電漿蝕刻處理。其實驗結果示於圖3。橫軸表示2種氣體之比率，縱軸表示蝕刻速率。越往曲線之右側走，溴化氫HBr相對於三氯化硼BCl3 之比率就越高。(Experiment 2 vs. gas species of zirconia film: ratio of BCl 3 to HBr) Next, the inventor's team changed the ratio between boron trichloride BCl 3 and hydrogen bromide to perform plasma etching treatment. . The experimental results are shown in Figure 3. The horizontal axis represents the ratio of the two gases, and the vertical axis represents the etching rate. Go to the right side of the curve, the higher the ratio of boron trichloride BCl 3 with respect to the hydrogen bromide HBr.

其結果得知，越是增加溴化氫HBr相對於三氯化硼BCl3 之比率，則選擇比「ZrO／Ox」及選擇比「ZrO／CUL」越趨向提升。另外得知，氧化鋯膜之蝕刻速率「ZrO ER」取決於三氯化硼BCl3 之流量，若三氯化硼BCl3 的流量越多就會越高。三氯化硼BCl3 相對於溴化氫HBr之流量比，較佳係50％以下。尤其在三氯化硼BCl3 與溴化氫HBr的流量為「25／125」之時，氧化鋯膜的蝕刻速率「ZrO ER」就會在容許值以上，且選擇比「ZrO／Ox」及選擇比「ZrO／CUL」皆為高而佳。As a result, it was found that the more the ratio of hydrogen bromide HBr to boron trichloride BCl 3 was increased, the more the ratio of "ZrO/Ox" and the selectivity ratio "ZrO/CUL" were increased. In addition that, the etch rate of the zirconium oxide film "ZrO ER" depends on the flow rate of boron trichloride BCl 3, if more boron trichloride BCl 3 flow rate will be higher. The flow ratio of boron trichloride BCl 3 to hydrogen bromide HBr is preferably 50% or less. In particular, when the flow rate of boron trichloride BCl 3 and hydrogen bromide HBr is "25/125", the etching rate "ZrO ER" of the zirconia film is above the allowable value, and the ratio of "ZrO/Ox" is selected. The choice is higher than "ZrO/CUL".

從以上結果得知，選擇比「ZrO／Ox」及選擇比「ZrO／CUL」之提升與氫H相關。再者得知，為了維持或提高蝕刻速率，需要三氯化硼BCl3 。因此，若考量蝕刻速率與選擇比雙方，則可知在本實施形態之圖案形成方法，較佳係使用在三氯化硼BCl3 添加了氫H成分的混合氣體。From the above results, it is known that the selection is higher than the "ZrO/Ox" and the selection is higher than the "ZrO/CUL". It is also known that in order to maintain or increase the etching rate, boron trichloride BCl 3 is required . Therefore, in consideration of both the etching rate and the selection ratio, it is preferable to use a mixed gas in which a hydrogen H component is added to boron trichloride BCl 3 in the pattern forming method of the present embodiment.

（實驗3相對於氧化鋯膜之氣體種類：BCl3 與HBr與H2 之比率） 有鑑於此，其次，本案發明人團隊使三氯化硼BCl3 的流量固定，變化溴化氫HBr與氫H2 之間的比率，而進行了電漿蝕刻處理。其實驗結果示於圖4。於此實驗結果，係將三氯化硼BCl3 的流量固定為「125sccm」，並變化溴化氫HBr與氫H2 之間的比率而進行電漿蝕刻處理。橫軸表示3種氣體之比率，縱軸表示蝕刻速率。越往曲線之右側走，氫H2 相對於溴化氫HBr之比率就越高。(Experiment 3 vs. zirconia film gas species: ratio of BCl 3 to HBr to H 2 ) In view of this, secondly, the inventor team fixed the flow rate of boron trichloride BCl 3 and changed hydrogen bromide HBr and hydrogen. The ratio between H 2 was subjected to plasma etching treatment. The experimental results are shown in Figure 4. As a result of this experiment, the flow rate of boron trichloride BCl 3 was fixed to "125 sccm", and the ratio between hydrogen bromide HBr and hydrogen H 2 was changed to perform plasma etching treatment. The horizontal axis represents the ratio of the three gases, and the vertical axis represents the etching rate. The more you go to the right of the curve, the higher the ratio of hydrogen H 2 to hydrogen bromide.

如此這般，得知若將溴化氫HBr一路置換成氫H2 ，選擇比「ZrO／Ox」及選擇比「ZrO／CUL」大致會提升。氫H2 的流量較佳係大於溴化氫HBr的流量。尤其選擇比「ZrO／Ox」係越將溴化氫HBr置換成氫H2 越高。也就是說，得知若提高混合氣體中之氫H的分壓，則選擇比「ZrO／Ox」及選擇比「ZrO／CUL」會變高。In this way, it is known that if hydrogen bromide HBr is replaced by hydrogen H 2 , the selectivity is higher than "ZrO/Ox" and the selectivity is higher than "ZrO/CUL". The flow rate of hydrogen H 2 is preferably greater than the flow rate of hydrogen bromide HBr. In particular, the higher the hydrogen bromide HBr is replaced by the "ZrO/Ox" system, the higher the H 2 is . That is, it is known that if the partial pressure of the hydrogen H in the mixed gas is increased, the selection ratio "ZrO/Ox" and the selection ratio "ZrO/CUL" become higher.

（實驗4相對於氧化鋯膜之氣體種類：BCl3 與H2 之比率） 有鑑於此，其次，本案發明人團隊變化三氯化硼BCl3 與氫H2 之間的比率，而進行了電漿蝕刻處理。其實驗結果示於圖5。於此實驗結果，係越往曲線之右側走，氫H2 相對於三氯化硼BCl3 之比率就越高。(Experiment 4 vs. zirconia film gas species: ratio of BCl 3 to H 2 ) In view of this, secondly, the inventor's team changed the ratio between boron trichloride BCl 3 and hydrogen H 2 and performed electricity. Slurry etching treatment. The experimental results are shown in Fig. 5. As a result of this experiment, the higher the ratio of hydrogen H 2 to boron trichloride BCl 3 , the more toward the right side of the curve.

其結果，三氯化硼BCl3 與氫H2 之流量，在「130／0」～「25／125」（皆為sccm）之任一情形下，選擇比「ZrO／Ox」及選擇比「ZrO／CUL」皆為良好。也就是說，三氯化硼BCl3 之流量較佳係少於氫H2 之流量。As a result, the flow rate of boron trichloride BCl 3 and hydrogen H 2 is selected in any of "130/0" to "25/125" (both sccm), and the ratio of "ZrO/Ox" and selection ratio is selected. ZrO/CUL" is good. That is to say, the flow rate of boron trichloride BCl 3 is preferably less than the flow rate of hydrogen H 2 .

尤其在三氯化硼BCl3 與氫H2 的流量，係「50／100」及「25／125」（皆為sccm）的情況下，選擇比「ZrO／Ox」及選擇比「ZrO／CUL」皆為無限大，最為良好。也就是說，三氯化硼BCl3 與氫H2 的流量在「50／100」及「25／125」（皆為sccm）的情況下，可以不切削到作為下層膜之矽氧化膜或非晶質碳膜，而僅蝕刻氧化鋯膜。Especially when the flow rate of boron trichloride BCl 3 and hydrogen H 2 is "50/100" and "25/125" (both sccm), choose "ZrO/Ox" and select ratio "ZrO/CUL". All are infinite and the best. That is to say, when the flow rate of boron trichloride BCl 3 and hydrogen H 2 is "50/100" and "25/125" (both sccm), the tantalum oxide film or the non-cut film may not be cut. The crystalline carbon film is etched only by the zirconia film.

基於以上之結果，於本實施形態之圖案形成方法，係由含有三氯化硼BCl3 與氫H2 的氣體產生電漿，使用形成有圖案之第1遮罩（例如，光阻膜），對含有氧化鋯膜的膜層進行電漿蝕刻。藉此，可以將形成有所要圖案之氧化鋯膜，用作為對矽氧化膜或非晶質碳膜進行電漿蝕刻之際的遮罩材料。藉此而可以進行良好的電漿蝕刻。Based on the above results, in the pattern forming method of the present embodiment, a plasma is generated from a gas containing boron trichloride BCl 3 and hydrogen H 2 , and a first mask (for example, a photoresist film) on which a pattern is formed is used. The film layer containing the zirconia film is subjected to plasma etching. Thereby, the zirconia film on which the desired pattern is formed can be used as a mask material for plasma etching of the tantalum oxide film or the amorphous carbon film. Thereby, good plasma etching can be performed.

蝕刻氧化鋯膜之際的第1遮罩，亦可使用矽氧化膜、非晶質碳膜或旋塗碳（spin on carbon）膜以取代光阻膜。在此情況下，可將三氯化硼BCl3 與氫H2 的流量設為「130／0」、「125／25」、「100／50」、「75／75」、「50／100」、「25／125」（皆為sccm）中之任一。其中，若使三氯化硼BCl3 與氫H2 的流量為「50／100」或「25／125」（皆為sccm），則可以使選擇比「ZrO／Ox」及選擇比「ZrO／CUL」成為無限大，故最佳。In the first mask for etching the zirconia film, a tantalum oxide film, an amorphous carbon film, or a spin on carbon film may be used instead of the photoresist film. In this case, the flow rates of boron trichloride BCl 3 and hydrogen H 2 can be set to "130/0", "125/25", "100/50", "75/75", and "50/100". , "25/125" (all are sccm). Wherein, if the flow rate of boron trichloride BCl 3 and hydrogen H 2 is "50/100" or "25/125" (both sccm), the selection ratio "ZrO/Ox" and the selection ratio "ZrO/ can be made. CUL" is infinite, so it is the best.

（實驗5相對於氧化鋯膜之氣體種類：添加Ar氣體） 其次，本案發明人團隊，在三氯化硼BCl3 及氫H2 之氣體中，變化流量地添加氬Ar氣體以作為稀有氣體之一例，而進行了電漿蝕刻處理。其實驗結果示於圖6。(Experiment 5 vs. zirconia film gas type: addition of Ar gas) Next, the inventor's team added argon Ar gas as a rare gas in a gas flow rate of boron trichloride BCl 3 and hydrogen H 2 . In one example, a plasma etching process was performed. The experimental results are shown in Fig. 6.

在此實驗，係將三氯化硼BCl3 及氫H2 的流量固定為「50sccm」及「100sccm」，而使氬Ar的流量變化成「0」、「150」、「300」（皆為sccm）。其結果得知，在以150sccm添加氬Ar氣體的情況下，相較於不添加氬Ar氣體的情況，氧化鋯膜之蝕刻速率「ZrO ER」有所提升。再者，不論是否添加氬Ar氣體，選擇比「ZrO／Ox」及選擇比「ZrO／CUL」不變，仍為無限大。因此，若適量地添加氬Ar氣體，則氧化鋯膜的蝕刻速率「ZrO ER」會提升，而選擇比「ZrO／Ox」及選擇比「ZrO／CUL」仍會維持在最佳狀態。In this experiment, the flow rates of boron trichloride BCl 3 and hydrogen H 2 were fixed to "50 sccm" and "100 sccm", and the flow rate of argon Ar was changed to "0", "150", and "300" (both Sccm). As a result, it was found that when argon Ar gas was added at 150 sccm, the etching rate "ZrO ER" of the zirconia film was improved as compared with the case where argon Ar gas was not added. Furthermore, regardless of whether or not argon Ar gas is added, the selection ratio is "ZrO/Ox" and the selection ratio is "ZrO/CUL", which is still infinite. Therefore, when an argon Ar gas is appropriately added, the etching rate "ZrO ER" of the zirconia film is increased, and the selection ratio "ZrO/Ox" and the selection ratio "ZrO/CUL" are maintained at an optimum state.

（實驗6相對於氧化鋯膜之氣體種類：添加He氣體） 本案發明人團隊，作為稀有氣體之一例，亦針對氦He氣體進行了同樣的實驗。也就是說，在三氯化硼BCl3 及氫H2 之氣體中，變化流量地添加氦He氣體，而進行了電漿蝕刻處理。其實驗結果示於圖7。(Experiment 6: Gas type with respect to zirconia film: He gas was added) The inventor of the present invention conducted the same experiment for 氦He gas as an example of a rare gas. That is, in the gas of boron trichloride BCl 3 and hydrogen H 2 , 氦He gas was added at a variable flow rate, and plasma etching treatment was performed. The experimental results are shown in Fig. 7.

在此實驗，係將三氯化硼BCl3 及氫H2 的流量固定為「50sccm」及「100sccm」，而使氦He的流量變化成「0」、「150」、「300」（皆為sccm）。其結果得知，在以150sccm或300sccm添加氦He氣體的情況下，相較於不添加氦He氣體的情況，氧化鋯膜之蝕刻速率「ZrO ER」有所提升。另一方面，若不添加氦He氣體，則選擇比「ZrO／Ox」及選擇比「ZrO／CUL」會係無限大，相較於添加了氦He氣體的情況係更佳；但不論是否添加氦He氣體，皆會獲得容許值以上的選擇比「ZrO／Ox」及選擇比「ZrO／CUL」。In this experiment, the flow rates of boron trichloride BCl 3 and hydrogen H 2 were fixed to "50 sccm" and "100 sccm", and the flow rate of helium He was changed to "0", "150", and "300" (both Sccm). As a result, it was found that when yttrium He gas was added at 150 sccm or 300 sccm, the etch rate "ZrO ER" of the zirconia film was improved as compared with the case where 氦He gas was not added. On the other hand, if 氦He gas is not added, the selection is infinitely larger than "ZrO/Ox" and the selection ratio "ZrO/CUL", which is better than the case where 氦He gas is added; however, whether or not it is added For 氦He gas, the selection ratio of "ZrO/Ox" and the selection ratio "ZrO/CUL" are obtained.

由上述可知，若對三氯化硼BCl3 及氫H2 的氣體加入氬Ar氣體或氦He氣體等稀有氣體，則可以在維持良好選擇比的同時，提升氧化鋯膜的蝕刻速率「ZrO ER」，而可以提升處理的產出量（throughput）。As described above, when a rare gas such as argon Ar gas or helium He gas is added to the gas of boron trichloride BCl 3 and hydrogen H 2 , the etching rate of the zirconium oxide film "ZrO ER can be improved while maintaining a good selection ratio. , and can increase the throughput of processing.

以上，針對在本實施形態之圖案形成方法，為分析出適用於在氧化鋯膜上形成所要圖案之際的氣體種類，所進行之實驗的結果，進行了說明。透過該實驗，得知藉由使含有三氯化硼BCl3 與氫H2 的混合氣體電漿化而對氧化鋯膜進行電漿蝕刻，可以提高氧化鋯膜之蝕刻速率「ZrO ER」，且可以提高氧化鋯膜相對於作為下層膜之矽氧化膜或非晶質碳膜的選擇比。As described above, in the pattern forming method of the present embodiment, the results of experiments conducted to analyze the types of gases applied to the desired pattern on the zirconia film have been described. Through this experiment, it was found that the plasma etching of the zirconia film by plasma-mixing a mixed gas containing boron trichloride BCl 3 and hydrogen H 2 can increase the etching rate "ZrO ER" of the zirconia film, and The selection ratio of the zirconia film to the tantalum oxide film or the amorphous carbon film as the underlayer film can be increased.

根據發明人團隊的實驗，在所導入之氣體之中，藉由三氯化硼BCl3 所含有的氯Cl成分，可以提高氧化鋯膜的蝕刻速率「ZrO ER」。再者，藉由提高導入之氣體內所含有之氫H的分壓，可以提高氧化鋯膜相對於作為下層膜之矽氧化膜或非晶質碳膜的選擇比（選擇比「ZrO／Ox」及選擇比「ZrO／CUL」）。又，在下層膜係旋塗碳膜的情況下亦與非晶質碳膜相同，可以提高氧化鋯膜相對於旋塗碳膜的選擇比。According to experiments by the inventors' team, the etching rate "ZrO ER" of the zirconia film can be increased by the chlorine Cl component contained in the boron trichloride BCl 3 among the introduced gases. Further, by increasing the partial pressure of the hydrogen H contained in the introduced gas, the selection ratio of the zirconia film to the tantalum oxide film or the amorphous carbon film as the underlayer film can be increased (selection ratio "ZrO/Ox" And choose the ratio "ZrO/CUL"). Further, in the case where the underlying film is spin-coated with a carbon film, as in the case of the amorphous carbon film, the selection ratio of the zirconia film to the spin-on carbon film can be improved.

以上針對一種圖案形成方法進行了說明，該方法包含以下步驟：導入第1氣體，藉由前述第1氣體所產生之電漿，使用形成有圖案之第1遮罩而蝕刻含有氧化鋯膜之膜層，以在該氧化鋯膜上形成圖案之步驟。此外，針對在圖案形成方法中所使用之第1氣體的最佳化，進行了說明。The method for forming a pattern is described above. The method includes the steps of: introducing a first gas, etching a film containing a zirconium oxide film by using a plasma generated by the first gas, using a first mask formed with a pattern; a layer to form a pattern on the zirconia film. Further, the optimization of the first gas used in the pattern forming method has been described.

於上述實驗中，作為第1氣體所含有的氣體之一，使用了三氯化硼BCl3 。然而，第1氣體所含有的氣體，並不限於三氯化硼BCl3 。於第1氣體，只要至少包含含有鹵素之氣體即可。含有鹵素之氣體，發揮用以蝕刻氧化鋯膜之氣體的功能。作為含有鹵素之氣體的例子，可以係包含下述中至少一個含氯化物氣體：三氯化硼BCl3 、四氯化碳CCl4 、氯Cl2 及四氯化矽SiCl4 。作為含有鹵素之氣體的其他例子，可以係含有含溴氣體或含氟氣體。In the above experiment, boron trichloride BCl 3 was used as one of the gases contained in the first gas. However, the gas contained in the first gas is not limited to boron trichloride BCl 3 . The first gas may be at least a gas containing a halogen. The halogen-containing gas functions as a gas for etching the zirconia film. As an example of the halogen-containing gas, at least one of the following chloride-containing gases may be contained: boron trichloride BCl 3 , carbon tetrachloride CCl 4 , chlorine chloride 2 , and hafnium tetrachloride SiCl 4 . As another example of the halogen-containing gas, a bromine-containing gas or a fluorine-containing gas may be contained.

例如，於上述實驗中，係使第1氣體含有溴化氫HBr或氫H2 氣體。然而，第1氣體所含有的氣體，並不限於溴化氫HBr或氫H2 氣體，只要係含氫氣體即可。含氫氣體在蝕刻氧化鋯膜之際，發揮作為提高選擇比之氣體的功能。作為含氫氣體的例子，可以含有以下至少一種氣體：溴化氫HBr、氫H2 及甲烷CH4 。For example, in the above experiment, the first gas contains hydrogen bromide HBr or hydrogen H 2 gas. However, the gas contained in the first gas is not limited to hydrogen bromide HBr or hydrogen H 2 gas, and may be a hydrogen-containing gas. The hydrogen-containing gas functions as a gas for increasing the selectivity when the zirconia film is etched. As an example of the hydrogen-containing gas, at least one of the following gases may be contained: hydrogen bromide HBr, hydrogen H 2 , and methane CH 4 .

更進一步而言，為了更為提高氧化鋯膜的蝕刻速率，於第1氣體中，在含有鹵素之氣體之外，亦可含有稀有氣體。稀有氣體，只要係含有氬Ar氣體及氦He氣體中之至少一種即可。Furthermore, in order to further increase the etching rate of the zirconia film, a rare gas may be contained in the first gas in addition to the halogen-containing gas. The rare gas may be at least one of argon Ar gas and helium He gas.

又，以第1氣體對氧化鋯膜進行電漿蝕刻之際所使用之第1遮罩，可以係光阻遮罩，亦可以係矽氧化膜，也可以係非晶質碳膜。Further, the first mask used for plasma etching the zirconia film by the first gas may be a photoresist mask, or may be an oxide film or an amorphous carbon film.

又，上述實驗1～實驗6之製程條件，列示如下。 壓力                  ：20mT 第1高頻電力    ：500W 第2高頻電力    ：100W 載置台溫度      ：30℃ 蝕刻時間          ：30s ［電漿蝕刻方法］ 在上述本實施形態之圖案形成方法，係藉由包含含有鹵素之氣體的氣體所產生之電漿，而在氧化鋯膜上形成圖案。圖案化後之氧化鋯膜，可良好適用於對作為下層膜之矽氧化膜或非晶質碳膜進行電漿蝕刻所用的遮罩。藉由使用氧化鋯膜作為遮罩材料，可以使遮罩選擇比提升，並在矽氧化膜等形成深且垂直的深孔。以下將針對包含氧化鋯膜之圖案形成步驟的本實施形態相關電漿蝕刻方法，參照圖8及圖9以進行說明。Further, the process conditions of the above Experiments 1 to 6 are listed below. Pressure: 20 mT First high frequency power: 500 W Second high frequency power: 100 W Mounting table temperature: 30 ° C Etching time: 30 s [plasma etching method] The pattern forming method according to the above embodiment includes halogen-containing The plasma produced by the gas of the gas forms a pattern on the zirconia film. The patterned zirconium oxide film is suitably used for a mask for plasma etching of a tantalum oxide film or an amorphous carbon film as an underlayer film. By using a zirconia film as a mask material, the mask selection ratio can be increased, and a deep and vertical deep hole can be formed in the tantalum oxide film or the like. Hereinafter, a plasma etching method according to this embodiment including a pattern forming step of a zirconium oxide film will be described with reference to FIGS. 8 and 9.

圖8係繪示本實施形態之電漿蝕刻方法的執行程序的流程圖。圖9係繪示本實施形態之電漿蝕刻中，各膜層之蝕刻狀態的圖。Fig. 8 is a flow chart showing the execution procedure of the plasma etching method of the embodiment. Fig. 9 is a view showing an etching state of each film layer in plasma etching in the embodiment.

本實施形態之電漿蝕刻方法，係由圖1之控制部7，根據記載有本實施形態之電漿蝕刻方法之執行程序的製程配方，控制電漿蝕刻裝置1而實現。The plasma etching method of the present embodiment is realized by controlling the plasma etching apparatus 1 by the control unit 7 of Fig. 1 in accordance with the process recipe in which the execution procedure of the plasma etching method of the present embodiment is described.

一旦開始電漿蝕刻處理，就會將晶圓W搬入處理室C內（S10）。對於搬入之晶圓W，例如圖9（a）所示，依序積層矽膜106、矽氧化膜104（或非晶質碳膜）、氧化鋯膜102、第1遮罩100。第1遮罩100係例如形成有所要圖案之光阻膜。Once the plasma etching process is started, the wafer W is carried into the processing chamber C (S10). For the loaded wafer W, for example, as shown in FIG. 9(a), the tantalum film 106, the tantalum oxide film 104 (or amorphous carbon film), the zirconium oxide film 102, and the first mask 100 are sequentially laminated. The first mask 100 is, for example, a photoresist film having a desired pattern.

接著，導入第1氣體，並由第1高頻電源5施加產生電漿用的高頻電力，藉此而產生出電漿（S12）。作為第1氣體之一例，可舉三氯化硼BCl3 及氫H2 。又，會由第2高頻電源6施加偏壓用的高頻電力。Then, the first gas is introduced, and the high-frequency power for generating plasma is applied from the first high-frequency power source 5, whereby plasma is generated (S12). Examples of the first gas include boron trichloride BCl 3 and hydrogen H 2 . Further, high frequency power for biasing is applied by the second high frequency power source 6.

接著，藉由第1氣體所產生之電漿，使用第1遮罩以蝕刻氧化鋯膜（S14）。藉此在氧化鋯膜上，形成所要的圖案。例如，如圖9（b）所示，氧化鋯膜102會成為形成有所要圖案之狀態。Next, the first mask is used to etch the zirconia film by the plasma generated by the first gas (S14). Thereby, a desired pattern is formed on the zirconia film. For example, as shown in FIG. 9(b), the zirconia film 102 is in a state in which a desired pattern is formed.

接著，導入第2氣體，並由第1高頻電源5施加產生電漿用的高頻電力，藉此而產生出電漿（S16）。Then, the second gas is introduced, and high-frequency electric power for generating plasma is applied from the first high-frequency power source 5, whereby plasma is generated (S16).

作為第2氣體之一例，在所要蝕刻之膜係矽氧化膜的情況下，可舉：C4 F6 、C4 F8 、O2 、Ar、NF3 、CF4 、SF6 等。在所要蝕刻之膜係有機膜的情況下，可舉HBr、CO2 、He、N2 、H2 、O2 、Ar、COS、Cl2 、CF4 、CHF3 、SF6 等。As an example of the second gas, in the case of a film-based oxide film to be etched, C 4 F 6 , C 4 F 8 , O 2 , Ar, NF 3 , CF 4 , SF 6 or the like can be given. In the case of the film-based organic film to be etched, HBr, CO 2 , He, N 2 , H 2 , O 2 , Ar, COS, Cl 2 , CF 4 , CHF 3 , SF 6 or the like can be given.

接著，藉由第2氣體所產生之電漿，以圖案化後的氧化鋯膜作為第2遮罩，進行蝕刻（S18）。藉此，例如圖9（c）所示，矽氧化膜104（或非晶質碳膜）就會蝕刻成所要的圖案。Next, the patterned zirconium oxide film is used as a second mask by the plasma generated by the second gas, and etching is performed (S18). Thereby, for example, as shown in FIG. 9(c), the tantalum oxide film 104 (or amorphous carbon film) is etched into a desired pattern.

接著，判定預先決定之既定批次數量的晶圓處理是否已全部結束（S20）。在判定尚未結束既定批次數量之晶圓處理的情況下，就回到S10，搬入下一枚晶圓W，重覆S12～S20之處理。於S20判定已結束既定批次數量之晶圓處理的情況下，結束本處理。Next, it is determined whether or not the wafer processing of the predetermined number of batches determined in advance has all been completed (S20). When it is determined that the wafer processing of the predetermined batch number has not been completed, the process returns to S10, and the next wafer W is carried in, and the processes of S12 to S20 are repeated. When it is determined in S20 that the wafer processing of the predetermined batch number has been completed, the processing is terminated.

以上，針對以氧化鋯膜作為遮罩而對下層膜進行乾蝕刻的方法，進行了說明。若依據本實施形態之電漿蝕刻方法，可以使用相對於矽氧化膜104或非晶質碳膜具有良好選擇比的氧化鋯膜作為遮罩材料，而良好地進行電漿蝕刻。As described above, a method of dry etching the underlayer film using a zirconia film as a mask has been described. According to the plasma etching method of the present embodiment, a zirconia film having a good selection ratio with respect to the tantalum oxide film 104 or the amorphous carbon film can be used as a mask material, and plasma etching can be favorably performed.

［清洗方法］ 於圖9（a）所示之圖案形成（電漿蝕刻）步驟、及圖9（b）所示之電漿蝕刻步驟，會蝕刻氧化鋯膜。如此一來，處理室內會附著氧化鋯含有物。而氧化鋯含有物之附著物所造成之處理室內的經時變化，就會成為導致發生製程偏移（process shift）的主要原因。[Cleaning Method] The zirconia film is etched in the pattern forming (plasma etching) step shown in Fig. 9 (a) and the plasma etching step shown in Fig. 9 (b). As a result, the zirconia content is attached to the treatment chamber. The time-dependent change in the processing chamber caused by the deposit of the zirconia-containing material is a major cause of process shift.

有鑑於此，於本實施形態之清洗方法，會以含有第1氣體（例如：三氯化硼BCl3 及氫H2 ）之氣體，去除附著於處理室內之氧化鋯含有物。In view of this, in the cleaning method of the present embodiment, the zirconia-containing material adhering to the processing chamber is removed by a gas containing a first gas (for example, boron trichloride BCl 3 and hydrogen H 2 ).

圖10係繪示用以執行本實施形態之清洗方法之執行程序的流程圖。一旦開始電漿蝕刻處理，就會將擋片晶圓搬入處理室C內（S30）。但是，亦可不搬入擋片晶圓。在此種情況下，會進行WLDC（無晶圓乾式清洗）。Fig. 10 is a flow chart showing the execution procedure for executing the cleaning method of the embodiment. Once the plasma etching process is started, the shutter wafer is carried into the processing chamber C (S30). However, it is also possible not to carry the spacer wafer. In this case, WLDC (Wrap Without Dry Cleaning) is performed.

接著，導入第1氣體，並由第1高頻電源5施加產生電漿用的高頻電力，藉此而產生出電漿（S32）。藉由第1氣體所產生之電漿，將附著於處理室內之氧化鋯含有物加以去除，而對處理室C內進行清洗（S34）。藉此，去除因對氧化鋯膜進行電漿蝕刻而附著於處理室內壁之氧化鋯含有物，而得以清洗處理室C內部。Then, the first gas is introduced, and the high-frequency power for generating plasma is applied from the first high-frequency power source 5, whereby plasma is generated (S32). The zirconia-containing material adhering to the processing chamber is removed by the plasma generated by the first gas, and the inside of the processing chamber C is cleaned (S34). Thereby, the zirconia-containing material adhering to the inner wall of the processing chamber by plasma etching of the zirconia film is removed, and the inside of the processing chamber C can be cleaned.

又，使用於上述清洗之製程條件，列示如下。 壓力                  ：20mT 第1高頻電力    ：500W 載置台溫度      ：30℃ 蝕刻時間          ：30s 如上述說明所載，若藉由本實施形態之電漿蝕刻方法，可以在相對於矽氧化膜或非晶質碳等特定之所要蝕刻之膜的選擇比成為1以上的狀態下，對氧化鋯膜或包含氧化鋯膜的High－k膜進行電漿蝕刻。再者，可以在相對於矽氧化膜或非晶質碳等特定之所要蝕刻之膜的選擇比成為1以上的狀態下，在氧化鋯膜或High－k膜上形成圖案。再者，可以在相對於矽氧化膜或非晶質碳等特定之所要蝕刻之膜的選擇比成為1以上的狀態下，良好地清洗對氧化鋯膜或High－k膜進行電漿蝕刻後之處理室內部。Further, the process conditions used for the above cleaning are listed below. Pressure: 20 mT First high frequency power: 500 W Mounting table temperature: 30 ° C Etching time: 30 s As described above, the plasma etching method of the present embodiment can be used for the tantalum oxide film or amorphous carbon. The zirconia film or the High-k film containing the zirconia film is plasma-etched in a state where the selection ratio of the film to be etched is 1 or more. In addition, a pattern may be formed on the zirconia film or the High-k film in a state where the selection ratio of the film to be etched, such as the tantalum oxide film or the amorphous carbon, is 1 or more. In addition, it is possible to satisfactorily clean the zirconia film or the high-k film by plasma etching in a state in which the specific ratio of the film to be etched such as the tantalum oxide film or the amorphous carbon is one or more. Handle the interior of the room.

以上，藉由一實施形態，說明了電漿蝕刻方法、圖案形成方法及清洗方法，但本發明並不限定於上述實施形態，可以在本發明之範圍內實施各種變形及改良。As described above, the plasma etching method, the pattern forming method, and the cleaning method have been described in one embodiment. However, the present invention is not limited to the above embodiment, and various modifications and improvements can be made within the scope of the invention.

作為在本發明之電漿蝕刻裝置產生電漿之手段，並不限於用在上述實施形態之說明的電漿蝕刻裝置（電容耦合型電漿（CCP：Capacitively Coupled Plasma）產生手段），亦可以使用：電感耦合型電漿（ICP：Inductively Coupled Plasma）產生手段、螺旋波激發型電漿（HWP：Helicon Wave Plasma）產生手段、包含徑向線槽天線所產生之微波電漿或SPA（Slot Plane Antenna）電漿之微波激發表面波電漿產生手段、電子迴旋共振電漿（ECR：Electron Cyclotron Resonance Plasma）產生手段、使用上述產生手段之遠距電漿產生手段等。The means for generating plasma in the plasma etching apparatus of the present invention is not limited to the plasma etching apparatus (Capacitively Coupled Plasma) which is described in the above embodiment, and may be used. : Inductively Coupled Plasma (ICP), Spiral Wave Excited Plasma (HWP: Helicon Wave Plasma), Microwave Plasma or SPA (Slot Plane Antenna) The microwave-excited surface wave plasma generating means of the plasma, the electron cyclotron resonance plasma (ECR: Electron Cyclotron Resonance Plasma) generating means, the remote plasma generating means using the above-mentioned generating means, and the like.

於本發明實施處理之被處理體，並不限於在上述實施形態之說明所使用之（半導體）晶圓，亦可係例如：平板顯示器（Flat Panel Display）用的大型基板、EL元件或太陽電池用的基板。The object to be processed according to the present invention is not limited to the (semiconductor) wafer used in the description of the above embodiment, and may be, for example, a large substrate for a flat panel display, an EL element, or a solar cell. The substrate used.

1‧‧‧電漿蝕刻裝置
2‧‧‧載置台（下部電極）
3‧‧‧上部電極
3a‧‧‧擴散室
3b‧‧‧氣體孔
4‧‧‧氣體供給源
5‧‧‧第1高頻電源
6‧‧‧第2高頻電源
7‧‧‧控制部
7a‧‧‧CPU
7b‧‧‧ROM
7c‧‧‧CPU
100‧‧‧第1遮罩
102‧‧‧氧化鋯膜
104‧‧‧矽氧化膜
106‧‧‧矽膜
C‧‧‧處理室
W‧‧‧晶圓
S10、S12、S14、S16、S18、S20、S30、S32、S34‧‧‧步驟1‧‧‧ plasma etching device
2‧‧‧mounting table (lower electrode)
3‧‧‧Upper electrode
3a‧‧‧Diffuse room
3b‧‧‧ gas hole
4‧‧‧ gas supply source
5‧‧‧1st high frequency power supply
6‧‧‧2nd high frequency power supply
7‧‧‧Control Department
7a‧‧‧CPU
7b‧‧‧ROM
7c‧‧‧CPU
100‧‧‧1st mask
102‧‧‧Zirconium oxide film
104‧‧‧矽Oxide film
106‧‧‧矽膜
C‧‧‧Processing room
W‧‧‧ wafer
S10, S12, S14, S16, S18, S20, S30, S32, S34‧‧

【圖1】繪示一實施形態之電漿蝕刻裝置之概略結構的縱剖面圖。 【圖2】依照一實施形態之氣體種類，針對氧化鋯膜與下層膜（Ox／CUL）之ER及選擇比的實驗結果。 【圖3】依照一實施形態之BCl3 與HBr間的比率，針對氧化鋯膜與下層膜（Ox／CUL）之ER及選擇比的實驗結果。 【圖4】依照一實施形態之HBr與H2 間的比率，針對氧化鋯膜與下層膜（Ox／CUL）之ER及選擇比的實驗結果。 【圖5】依照一實施形態之BCl3 與H2 間的比率，針對氧化鋯膜與下層膜（Ox／CUL）之ER及選擇比的實驗結果。 【圖6】對一實施形態之BCl3 與H2 添加Ar之情況下，氧化鋯膜與下層膜（Ox／CUL）之ER及選擇比的實驗結果。 【圖7】對一實施形態之BCl3 與H2 添加He之情況下，氧化鋯膜與下層膜（Ox／CUL）之ER及選擇比的實驗結果。 【圖8】繪示一實施形態之電漿蝕刻方法的執行程序的流程圖。 【圖9】（a）、（b）、（c）繪示一實施形態之電漿蝕刻中，各膜層之蝕刻狀態的圖。 【圖10】用以執行一實施形態之清洗處理的流程圖。Fig. 1 is a longitudinal cross-sectional view showing a schematic configuration of a plasma etching apparatus according to an embodiment. Fig. 2 is an experimental result of the ER and the selection ratio of the zirconia film and the underlayer film (Ox/CUL) according to the gas type of one embodiment. Fig. 3 is a graph showing experimental results of ER and selection ratio of zirconia film and underlayer film (Ox/CUL) according to the ratio between BCl 3 and HBr according to an embodiment. Fig. 4 is a graph showing experimental results of ER and selection ratio of zirconia film and underlayer film (Ox/CUL) according to the ratio between HBr and H 2 according to an embodiment. Fig. 5 is a graph showing experimental results of ER and selection ratio of zirconia film and underlayer film (Ox/CUL) according to the ratio between BCl 3 and H 2 in one embodiment. Fig. 6 shows experimental results of ER and selection ratio of zirconia film and underlayer film (Ox/CUL) in the case where Ar is added to BCl 3 and H 2 of one embodiment. Fig. 7 shows experimental results of ER and selection ratio of zirconia film and underlayer film (Ox/CUL) in the case where He is added to BCl 3 and H 2 of one embodiment. FIG. 8 is a flow chart showing an execution procedure of a plasma etching method according to an embodiment. Fig. 9 (a), (b) and (c) are views showing an etching state of each film layer in plasma etching according to an embodiment. Fig. 10 is a flow chart for performing the cleaning process of an embodiment.

Claims (12)

一種電漿蝕刻方法，包括一步驟，其藉由三氯化硼BCl3 或四氯化矽SiCl4 中之任一者、與溴化氫HBr構成之氣體所產生之電漿，而對包含氧化鋯膜之膜層進行蝕刻，以蝕刻成在第1遮罩上所形成之所要的圖案；在該電漿蝕刻方法， 該氧化鋯膜之基底膜係矽氧化膜或非晶質碳，而氧化鋯膜相對於該基底膜的蝕刻選擇比係1以上。A plasma etching method comprising a step of oxidizing by a plasma generated by a gas composed of boron trichloride BCl 3 or hafnium tetrachloride SiCl 4 and hydrogen bromide HBr The film of the zirconium film is etched to be etched into a desired pattern formed on the first mask; in the plasma etching method, the base film of the zirconia film is oxidized or amorphous carbon, and oxidized The etching selectivity of the zirconium film with respect to the base film is 1 or more. 一種電漿蝕刻方法，包括一步驟，其藉由三氯化硼BCl3 與溴化氫HBr構成之氣體所產生之電漿，而對包含氧化鋯膜之膜層進行蝕刻，以蝕刻成在第1遮罩上所形成之所要的圖案；在該電漿蝕刻方法， 該氧化鋯膜之基底膜係矽氧化膜或非晶質碳，而氧化鋯膜相對於該基底膜的蝕刻選擇比係1以上； 三氯化硼BCl3 相對於溴化氫HBr的流量比係50％以下。A plasma etching method comprising a step of etching a film layer containing a zirconium oxide film by etching a plasma generated by a gas composed of boron trichloride BCl 3 and hydrogen bromide HBr a desired pattern formed on the mask; in the plasma etching method, the base film of the zirconia film is an oxide film or amorphous carbon, and the etching selectivity ratio of the zirconia film to the base film is 1 Above; the flow ratio of boron trichloride BCl 3 to hydrogen bromide is less than 50%. 如申請專利範圍第1或2項之電漿蝕刻方法，其中， 該氣體所產生之電漿，包含氫H2 所構成之氣體所產生之電漿。The plasma etching method according to claim 1 or 2, wherein the plasma generated by the gas contains a plasma generated by a gas composed of hydrogen H 2 . 一種電漿蝕刻方法，包括一步驟，其藉由三氯化硼BCl3 及溴化氫HBr、以及氫H2 構成之氣體所產生之電漿，而對包含氧化鋯膜之膜層進行蝕刻，以蝕刻成在第1遮罩上所形成之所要的圖案；在該電漿蝕刻方法， 該氧化鋯膜之基底膜係矽氧化膜或非晶質碳，而氧化鋯膜相對於該基底膜的蝕刻選擇比係1以上； 氫H2 的流量大於溴化氫HBr的流量。A plasma etching method comprising a step of etching a film layer comprising a zirconia film by a plasma generated by a gas composed of boron trichloride BCl 3 , hydrogen bromide HBr, and hydrogen H 2 Etching to a desired pattern formed on the first mask; in the plasma etching method, the base film of the zirconia film is an oxide film or amorphous carbon, and the zirconia film is opposite to the base film The etching selection ratio is above 1; the flow rate of hydrogen H 2 is greater than the flow rate of hydrogen bromide HBr. 一種電漿蝕刻方法，包括一步驟，其藉由三氯化硼BCl3 、氯Cl2 或四氯化矽SiCl4 中之任一、以及氫H2 或甲烷CH4 中之任一構成之氣體所產生之電漿，而對包含氧化鋯膜之膜層進行蝕刻，以蝕刻成在第1遮罩上所形成之所要的圖案；在該電漿蝕刻方法， 該氧化鋯膜之基底膜係矽氧化膜或非晶質碳，而氧化鋯膜相對於該基底膜的蝕刻選擇比係1以上。A plasma etching method comprising a step of forming a gas of any one of boron trichloride BCl 3 , chlorine Cl 2 or hafnium tetrachloride SiCl 4 , and hydrogen H 2 or methane CH 4 a plasma generated, and etching a film layer comprising a zirconia film to be etched into a desired pattern formed on the first mask; in the plasma etching method, the base film system of the zirconia film An oxide film or amorphous carbon, and the etching selectivity of the zirconia film with respect to the base film is 1 or more. 一種電漿蝕刻方法，包括一步驟，其藉由三氯化硼BCl3 、以及氫H2 構成之氣體所產生之電漿，而對包含氧化鋯膜之膜層進行蝕刻，以蝕刻成在第1遮罩上所形成之所要的圖案；在該電漿蝕刻方法， 該氧化鋯膜之基底膜係矽氧化膜或非晶質碳，而氧化鋯膜相對於該基底膜的蝕刻選擇比係1以上； 三氯化硼BCl3 的流量小於氫H2 的流量。A plasma etching method comprising a step of etching a film layer comprising a zirconia film by etching a plasma generated by a gas composed of boron trichloride BCl 3 and hydrogen H 2 a desired pattern formed on the mask; in the plasma etching method, the base film of the zirconia film is an oxide film or amorphous carbon, and the etching selectivity ratio of the zirconia film to the base film is 1 Above; the flow rate of boron trichloride BCl 3 is less than the flow rate of hydrogen H 2 . 如申請專利範圍第1至6項中任一項之電漿蝕刻方法，其中，該氣體包含稀有氣體。The plasma etching method according to any one of claims 1 to 6, wherein the gas contains a rare gas. 如申請專利範圍第1、2、4至6項中任一項之電漿蝕刻方法，其中，該第1遮罩，係由光阻遮罩、矽氧化膜、非晶質碳膜或旋塗碳膜中之任一者所形成。The plasma etching method according to any one of claims 1, 2, 4 or 6, wherein the first mask is made of a photoresist mask, a tantalum oxide film, an amorphous carbon film or a spin coating. Formed by either of the carbon films. 如申請專利範圍第1、2、4至6項中任一項之電漿蝕刻方法，其中，更包括以下步驟： 導入第2氣體； 藉由該第2氣體所產生之電漿，並以該氧化鋯膜作為第2遮罩； 對作為該氧化鋯膜之下層膜的矽氧化膜、非晶質碳膜或旋塗碳膜進行蝕刻，以蝕刻成在該氧化鋯膜上所形成之所要圖案。The plasma etching method according to any one of claims 1, 2, 4 or 6, wherein the method further comprises the steps of: introducing a second gas; generating a plasma by the second gas; a zirconium oxide film as a second mask; an antimony oxide film, an amorphous carbon film or a spin-on carbon film as a film under the zirconia film is etched to be etched into a desired pattern formed on the zirconia film . 一種圖案形成方法，包括一步驟，係藉由如申請專利範圍第1至8項中任一項之電漿蝕刻方法，使用形成有圖案之第1遮罩，以蝕刻包含氧化鋯膜之膜層，而在該氧化鋯膜上形成圖案。A pattern forming method comprising the step of etching a film layer containing a zirconia film by using a plasma etching method according to any one of claims 1 to 8 using a patterned first mask And a pattern is formed on the zirconia film. 一種清洗方法，包括一步驟，對藉由如申請專利範圍第1至8項中任一項之電漿蝕刻方法蝕刻包含氧化鋯膜之膜層後的處理室內部，進行清洗。A cleaning method comprising the steps of: etching a chamber inside a processing chamber including a film layer of a zirconium oxide film by a plasma etching method according to any one of claims 1 to 8 and performing cleaning. 一種電漿蝕刻方法，包括一步驟，其藉由溴化氫HBr構成之氣體所產生之電漿，而對包含氧化鋯膜之膜層進行蝕刻，以蝕刻成在第1遮罩上所形成之所要的圖案；在該電漿蝕刻方法， 該氧化鋯膜之基底膜係非晶質碳，而氧化鋯膜相對於該基底膜之蝕刻選擇比係無限大。A plasma etching method comprising a step of etching a film layer comprising a zirconia film by etching a plasma generated by a gas composed of hydrogen bromide HBr to be etched into a first mask The desired pattern; in the plasma etching method, the base film of the zirconia film is amorphous carbon, and the etching selectivity of the zirconia film relative to the base film is infinite.
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